CN110452684A - Cadmium-free quantum dots and preparation method thereof - Google Patents
Cadmium-free quantum dots and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of cadmium-free quantum dots and preparation method thereof, the cadmium-free quantum dots include stratum nucleare and shell, the component of the material of the stratum nucleare includes P elements and phosphide element, the shell includes the hypostracum being coated on the stratum nucleare and the outer shell that is coated on the hypostracum, the material of the hypostracum is ZnSeS, and the material of the outer shell is ZnS；The particle size of the cadmium-free quantum dots is 6nm~12nm, and the radius of the stratum nucleare is 1.2nm~4.5nm, and for the wave-length coverage of the fluorescence emission peak of the cadmium-free quantum dots in 510nm~650nm, half-peak breadth is 35nm~40nm, and luminous efficiency is 70%~85%.The half-peak breadth of cadmium-free quantum dots of the invention is relatively narrow and luminous efficiency is higher.
Description
Technical field
The present invention relates to quantum dot preparation fields, more particularly to a kind of cadmium-free quantum dots and preparation method thereof.
Background technique
In last decade, semiconductor material development is swift and violent, and wherein the research of quantum dot causes the very big of domestic and international researcher
Interest becomes one of most active field of scientific study.In the research process of quantum dot, people are gradually focus of attention
Iii-v quantum dot (such as InP quantum dot) is shifted to from II-VI group quantum dot (such as CdSe quantum dot).Due to the stabilization of covalent bond
Property so that III-V quantum dot have good optical stability, and low toxicity, display, illumination, optical device, biomedicine,
The fields such as solar battery show wide application prospect.Wherein, InP quantum dot has good size-constrained effect, PL
Spectrum can be material more deep in III-V quantum dot with covering visible light wave band, the research of synthetic technology, but it is closed
II-VI group quantum dot is still lagged behind at quality, that is, has that half-peak breadth is wider, luminous efficiency is lower, synthesis technology is complicated and very
Hardly possible realizes the problems such as volume production.
Summary of the invention
Based on this, it is necessary to provide that a kind of half-peak breadth is relatively narrow and the higher cadmium-free quantum dots of luminous efficiency, while provide one
The preparation method of kind of synthesis technology simply and readily cadmium-free quantum dots of volume production.
A kind of cadmium-free quantum dots, including stratum nucleare and shell, the component of the material of the stratum nucleare include P elements and indium
Element, the shell include the hypostracum being coated on the stratum nucleare and the outer shell that is coated on the hypostracum, it is described in
The material of shell is ZnSeS, and the material of the outer shell is ZnS；The particle size of the cadmium-free quantum dots is 6nm~12nm,
The radius of the stratum nucleare is 1.2nm~4.5nm, the wave-length coverage of the fluorescence emission peak of the cadmium-free quantum dots 510nm~
650nm, half-peak breadth are 35nm~40nm, and luminous efficiency is 70%~85%.
In one of the embodiments, the radius of the stratum nucleare account for the radius of the cadmium-free quantum dots ratio be 40%~
75%.
In one of the embodiments, in the stratum nucleare, the molar ratio of the P elements and the phosphide element be (0.1~
3): 1.
A kind of preparation method of cadmium-free quantum dots, includes the following steps:
First indium source, the first phosphorus source are mixed with the first mixed liquor, and reacted at 70 DEG C~150 DEG C, it is anti-to obtain first
Liquid is answered, contains the first ligand, the first non-complexing solvent and optional crystal seed stabilizer in first mixed liquor；
Second indium source, the second phosphorus source are mixed with first reaction solution, and reacted at 200 DEG C~300 DEG C, obtains
Two reaction solutions；
Selenium source, the first sulphur source, second reaction solution and the second mixed liquor are mixed, and carried out at 200 DEG C~350 DEG C
Reaction obtains third reaction solution, contains the first zinc source, Ligands and the 6th non-Lip river bonding solvent in second mixed liquor；And
Second sulphur source, the second zinc source are mixed with the third reaction solution, and reacted at 200 DEG C~350 DEG C, is obtained
To quantum dot.
Described the step of mixing the first indium source, the first phosphorus source with the first mixed liquor, includes: in one of the embodiments,
Wiring solution-forming is distinguished into first indium source and the first phosphorus source, then are injected into simultaneously with the rate of 10mL/min~200mL/min
In first mixed liquor.
Described the step of mixing the second indium source, the second phosphorus source with first reaction solution in one of the embodiments,
It include: that second indium source and the second phosphorus source are distinguished into wiring solution-forming, then successively with V1、V2To VxRate divide x stage injection to arrive
In first reaction solution, wherein V1=0.1mL/min~1.5mL/min, the rate representation of m-stage are Vm, Vm/V1=1+
Mp-p, p=0.8~1.2.
It is described in one of the embodiments, to mix selenium source, the first sulphur source, second reaction solution and the second mixed liquor
The step of include: that second reaction solution is first injected by second mixed liquor with the rate of 10mL/min~400mL/min
In, then with the rate of 0.01mL/min~5mL/min the selenium source and the first sulphur source are injected into second mixed liquor.
Described the step of mixing in the second sulphur source, the second zinc source with the third reaction solution in one of the embodiments,
It include: that wiring solution-forming is distinguished into second sulphur source and the second zinc source, then successively with V1’、V2' to Vy' rate divide the y stage to infuse
It is mapped in the third reaction solution, wherein V1'=0.1mL/min~20mL/min, the rate representation of n-th order section are Vn', Vn’/
V1'=1+np '-p ', p '=0.8~1.2.
In one of the embodiments, first indium source and the second indium source be separately selected from oleic acid indium, carbonic acid indium,
At least one of indium nitrate, indium acetate, stearic acid indium, indium iodide, indium bromide, trimethyl indium, inidum chloride and tetradecylic acid indium.
First phosphorus source and the second phosphorus source are separately selected from three (dimethylamino) in one of the embodiments,
At least one of phosphine, three (diethylin) phosphines, three (trimethylsilyl) phosphines, tri octyl phosphine and tributylphosphine.
First zinc source and the second zinc source are separately selected from zinc laurate, Pork and beans in one of the embodiments,
Cool acid zinc, zinc dithiocarbamate, diethyl zinc, zinc methide, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, chlorine
Change zinc, zinc fluoride, zinc carbonate, zinc cyanide, zinc nitrate, zinc oleate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, caproic acid
Zinc, zinc octoate, zinc palmitate, ten sour zinc, zinc undecylenate, diethyldithio-carbamate zinc, Zinc diacetate dihydrate and tristearin
At least one of sour zinc.
First sulphur source and the second sulphur source are separately selected from sulphur simple substance, alkyl sulfide in one of the embodiments,
At least one of alcohol, six amino thioether of hydrogen sulfide and bis- (trimethyl silicon substrate) thioethers.
The selenium source is selected from trioctylphosphine selenizing phosphine, three (normal-butyl) selenizing phosphines, three (Zhong Ding in one of the embodiments,
Base) selenizing phosphine, three (tert-butyl) selenizing phosphines, trimethyl selenizing phosphine, triphenyl selenizing phosphine, diphenyl selenizing phosphine, phenylselenenylation phosphine,
Thricyclohexyl selenizing phosphine, cyclohexyl selenizing phosphine, the pungent selenol of 1-, 1- dodecane selenol, selenium phenol, selenium simple substance, hydrogen selenide, bis- (front threes
Base silicyl) at least one of selenides and selenourea.
In one of the embodiments, the first non-complexing solvent be selected from even hexichol, octadecylene, 19 alkene, icosa alkene,
At least one of lignocerane, docosane, eicosane, octadecane, atoleine and isotriacontane.
First ligand is selected from ten acid, undecenoic acid, lauric acid/dodecanoic acid, tridecanoic acid, 14 in one of the embodiments,
At least one of acid, hexadecylic acid, stearic acid, octadecyl phosphoric acid and oleic acid.
In one of the embodiments, the crystal seed stabilizer in octadecyl phosphoric acid and trioctylphosphine extremely
Few one kind.
First ligand, the first non-complexing solvent and the crystal seed stabilizer in one of the embodiments,
Molar ratio is 1:(2~20): (0~3).
The molar ratio in first indium source, first phosphorus source and first ligand is in one of the embodiments,
1:(0.1~3): (1~5).
The molar ratio of second indium source and second phosphorus source is 1:(0.5~2 in one of the embodiments).
In one of the embodiments, the selenium source, first sulphur source and first zinc source molar ratio be (1~
3): (1~3): 1.
In one of the embodiments, first zinc source, the Ligands and the 6th non-complexing solvent molar ratio
For 1:(0.5~2): (1~5).
Second sulphur source and the molar ratio in second zinc source are (0.1~1) in one of the embodiments: 1.
Above-mentioned cadmium-free quantum dots are using P elements and phosphide element as the component of core layer material, in stratum nucleare outer cladding inner casing
Layer ZnSeS, then outer shell ZnS is coated, it is regular by the growth course and shell thickness, available lattice structure of control nucleation
High-quality stratum nucleare, and then obtain good shell, so that the half-peak breadth of gained quantum dot is relatively narrow, luminous efficiency is higher.In addition, should
Quantum dot does not contain environmentally harmful cadmium element, has the advantages that environmentally protective.
Detailed description of the invention
Fig. 1 is the process flow chart of the preparation method of the cadmium-free quantum dots of an embodiment；
Fig. 2 is the ultraviolet-visible absorption spectroscopy and fluorescence spectra of the InP/ZnSeS/ZnS quantum dot in embodiment 1,
Middle solid line represents ultraviolet and visible absorption peak, and dotted line represents fluorescence emission peak.
Specific embodiment
To facilitate the understanding of the present invention, below by specific embodiment to invention is more fully described.It is specific real
The mode of applying gives preferred embodiment of the invention.But the invention can be realized in many different forms, and unlimited
In embodiment described herein.On the contrary, purpose of providing these embodiments is makes understanding to the disclosure
It is more thorough and comprehensive.
Unless otherwise defined, all technical and scientific terms used herein and belong to technical field of the invention
The normally understood meaning of technical staff is identical.Term as used herein in the specification of the present invention is intended merely to description tool
The purpose of the embodiment of body, it is not intended that in the limitation present invention.
The cadmium-free quantum dots of one embodiment, including stratum nucleare and shell, the component of the material of stratum nucleare include P elements
And phosphide element, shell include the hypostracum being coated on stratum nucleare and the outer shell that is coated on hypostracum, the material of hypostracum is
ZnSeS, the material of outer shell are ZnS；The particle size of cadmium-free quantum dots is 6nm~12nm, the radius of stratum nucleare be 1.2nm~
4.5nm, for the wave-length coverage of the fluorescence emission peak of cadmium-free quantum dots in 510nm~650nm, half-peak breadth is 35nm~40nm, is shone
Efficiency is 70%~85%.In addition, the wave-length coverage of the ultraviolet and visible absorption peak of cadmium-free quantum dots can be in 490nm~630nm.
Wherein, the wavelength of the fluorescence emission peak of cadmium-free quantum dots, half-peak breadth and luminous efficiency can be conventional using this field
Instrument test obtain.For example, the wavelength and half-peak breadth of the fluorescence emission peak of cadmium-free quantum dots can use fluorescence spectrophotometry
Measurement examination obtains, and luminous efficiency can be obtained using integrating sphere fluorescent quantum test system and test, the wave of ultraviolet and visible absorption peak
Length can test to obtain using ultraviolet-uisible spectrophotometer.
Wherein, the particle size of cadmium-free quantum dots refers to the three-dimensional length of the maximum of cadmium-free quantum dots, that is, in cadmium-free quantum dots
The corresponding distance between maximum two o'clock.The radius of stratum nucleare refers to the maximum of the centre distance stratum nucleare outer surface of quantum dot
Length.The particle size of cadmium-free quantum dots and the radius of stratum nucleare can be obtained by transmissioning electric mirror test.
Further, it is 40%~75% that the radius of stratum nucleare, which accounts for the ratio of the radius of cadmium-free quantum dots,.In above range
Cadmium-free quantum dots have suitable stratum nucleare accounting and shell thickness, are conducive to be further reduced lattice defect, improve the effect that shines
Rate.The radius of cadmium-free quantum dots is the half of its particle size.
Further, in stratum nucleare, the molar ratio of P elements and phosphide element is (0.1~3): 1.In stratum nucleare, P elements and indium
The lattice structure that stratum nucleare is formed by when element is within the scope of aforementioned proportion is symmetrical and complete, and stability is high, at the same be conducive into
One step reduces half-peak breadth and improves luminous efficiency.
The preparation method of the cadmium-free quantum dots of one embodiment includes the following steps: with reference to Fig. 1
Step S110: the first ligand, the first non-complexing solvent and optional crystal seed stabilizer are mixed, then are warming up to 90 DEG C
~130 DEG C, form the first mixed liquor.
Wherein, the first ligand plays the role of coordination stability, and the first non-complexing solvent plays dissolution and dispersion reactant
Effect, crystal seed stabilizer is conducive to further promote In and p-shaped at stable crystal seed.
Further, the molar ratio of the first ligand, the first non-complexing solvent and crystal seed stabilizer can be 1:(2~20):
(0~3).
In one embodiment, crystal seed stabilizer can in octadecyl phosphoric acid and trioctylphosphine at least one
Kind.
Step S120: the first indium source, the first phosphorus source are mixed with the first mixed liquor, and is carried out at 70 DEG C~150 DEG C
One reaction, obtains the first reaction solution.In the step, the first indium source reacts to obtain InP crystal seed with the first phosphorus source.
Further, the step of the first indium source, the first phosphorus source being mixed with the first mixed liquor includes: by the first indium source and the
One phosphorus source distinguishes wiring solution-forming, then is injected into the first mixed liquor simultaneously with the rate of 10mL/min~200mL/min.
In the step of the first indium source and the first phosphorus source difference wiring solution-forming, the second non-complexing solvent can be used first
The dissolution of indium source and wiring solution-forming, and the first phosphorus source is dissolved by simultaneously wiring solution-forming using third non-complexing solvent.Those skilled in the art
Member it is appreciated that the second non-complexing solvent and third non-complexing solvent be in order to dissolve or disperse the first indium source and the first phosphorus source,
When the first indium source and the first phosphorus source are solution, the second non-complexing solvent or third non-complexing solvent also be can be omitted.
First indium source and the first phosphorus source are injected into the first mixed liquor simultaneously with the rate of 10mL/min~200mL/min
Refer to, the first indium source is mixed with the first phosphorus source according to identical rate difference (simultaneously) injection first in above range
In liquid.The first indium source and the first phosphorus source are injected into simultaneously in the first mixed liquor using above-mentioned injection rate, are conducive to injecting
Moment forms hypersaturated state in the solution, to form crystal seed.
Further, the condition of the first reaction is preferred are as follows: temperature is 80 DEG C~120 DEG C, and the time is 1min~10min.On
It states and is conducive to the state that crystal seed is finally reached optimum balance in the condition and range of the first reaction, seed sized is more evenly distributed.
It further, further include by first before the step of mixing the first indium source, the first phosphorus source with the first mixed liquor
The step of mixed liquor degasification.The time of degasification can be 10min~90min, be further 10min~60min.It can be with after degasification
Carry out subsequent reactions under inert gas protection, inert gas can be for example nitrogen, argon gas etc..
Further, the molar ratio of the first indium source, the first phosphorus source and the first ligand can be 1:(0.1~3): (1~5).
Step S130: the second indium source, the second phosphorus source are mixed with the first reaction solution, and is carried out at 200 DEG C~300 DEG C
Two reactions, obtain the second reaction solution.In the step, the second indium source and further growth on the basis of InP crystal seed of the second phosphorus source,
Form InP nucleus.
Further, the step of the second indium source, the second phosphorus source being mixed with the first reaction solution includes: by the second indium source and the
Two phosphorus sources distinguish wiring solution-forming, then successively with V1、V2To VxRate divide x stage injection into first reaction solution, wherein V1
=0.1mL/min~1.5mL/min, the rate representation of m-stage are Vm, Vm/V1=1+mp-p, p=0.8~1.2.
With V1、V2To VxRate divide x stage injection to refer into first reaction solution, can according to injection volume and
Target absorption spike is long, and injection is equally divided into x stage, by the second indium source and the second phosphorus source with identical V1Respectively (simultaneously)
Start to inject into the first mixed liquor, then, adjusts injection rate, successively carry out V2To VxStage is until injection finishes.X is for example
It can be 3~5.M-stage refers to some any stage in x stage, works as Vm/V1When=1+mp-p, p=0.8~1.2, x
The injection rate in a stage is gradually accelerated with a stable amplification, for example, works as V1=0.1mL/min and p=1
When, then V2=0.2mL/min, V3=0.3mL/min, V4=0.4mL/min, and so on.That is, in the injection process,
Second indium source and the second phosphorus source with identical rate and are always that the rate gradually increased is injected into the first reaction solution.Using
Such injection system can make reaction solution be constantly in optimal equilibrium state, promote homogeneous nucleation, obtained nucleus
Size distribution maintain it is identical as the size distribution of crystal seed.
Further, in the step of wiring solution-forming being distinguished in the second indium source and the second phosphorus source, the 4th non-complexing can be used
Second phosphorus source is dissolved simultaneously wiring solution-forming by the dissolution of the second indium source and wiring solution-forming, and using the 5th non-complexing solvent by solvent.When
When second indium source and the second phosphorus source are solution, the 4th non-complexing solvent or the 5th non-complexing solvent be can be omitted.
Further, the condition of the second reaction is preferred are as follows: temperature is 250 DEG C~280 DEG C, and the time is 30min~60min.
The condition and range of above-mentioned second reaction is conducive to the growth of nucleus, and stable and uniform quantum dot core can be prepared.
Further, the molar ratio of the second indium source and the second phosphorus source can be 1:(0.5~2).
Step S140: the first zinc source, Ligands and the 6th non-complexing solvent being mixed, then are warming up to 50 DEG C~250 DEG C,
Obtain the second mixed liquor.
Further, in step S140, temperature is preferably 100 DEG C~200 DEG C.
Further, the molar ratio of the first zinc source, Ligands and the 6th non-complexing solvent can be 1:(0.5~2): (1
~5).
Step S150: selenium source, the first sulphur source, the second reaction solution and the second mixed liquor are mixed, and at 200 DEG C~350 DEG C
Lower progress third reaction, obtains third reaction solution.
Further, by selenium source, the first sulphur source, the second reaction solution and the second mixed liquor mix the step of include: first with
Second reaction solution is injected into the second mixed liquor by the rate of 10mL/min~400mL/min, then with 0.01mL/min~5mL/
Selenium source and the first sulphur source are injected into the second mixed liquor by the rate of min.
Selenium source and the first sulphur source are injected into the second mixed liquor with the rate of 0.01mL/min~5mL/min and referred to, it will
Selenium source and the first sulphur source are injected in the second mixed liquor according to an identical rate difference (simultaneously) in above range.Using upper
State the quantum dot that injection rate advantageously forms uniform particle diameter.
Further, the condition of third reaction is preferred are as follows: temperature is 270 DEG C~330 DEG C, and the time is 10min~45min.
Further, it before the step of mixing selenium source, the first sulphur source, the second reaction solution and the second mixed liquor, also wraps
The step of including the second mixed liquor degasification.The condition of degasification can be with are as follows: temperature is 100 DEG C~150 DEG C, the time be 10min~
90min。
Further, selenium source, the first sulphur source and the molar ratio in the first zinc source can be (1~3): (1~3): 1.
Step S160: the second sulphur source, the second zinc source are mixed with third reaction solution, and is carried out at 200 DEG C~350 DEG C
Four reactions, obtain the 4th reaction solution.
Further, the condition of the 4th reaction is preferred are as follows: temperature is 270 DEG C~330 DEG C, and the time is 40min~120min.
Further, the step of the second sulphur source, the second zinc source being mixed with third reaction solution includes: by the second sulphur source and the
Wiring solution-forming is distinguished in two zinc sources, then successively with V1’、V2' to Vy' rate divide y stage injection into the third reaction solution,
Middle V1'=0.1mL/min~20mL/min, the rate representation of n-th order section are Vn', Vn’/V1'=1+np '-p ', p '=0.8~
1.2。
With V1’、V2' to Vy' rate divide y stage injection to refer into the third reaction solution, according to injection volume and mesh
Fluorescence emission peak wavelength is marked, injection is equally divided into y stage, by the second sulphur source and the second zinc source with identical V1' (same respectively
When) start to inject into third mixed liquor, then, injection rate is adjusted, V is successively carried out2' to Vy' stage until injection finish.y
It such as can be 3~10.N-th order section refers to some any stage in y stage, works as Vn’/V1'=1+np '-p ', p '=0.8
When~1.2, the injection rate in y stage is gradually accelerated with a stable amplification, for example, works as V1'=0.1mL/
Min and when p '=1, then V2'=0.2mL/min, V3'=0.3mL/min, V4'=0.4mL/min, and so on.That is,
In the injection process, the second sulphur source and the second zinc source with identical rate and are always that the rate gradually increased is injected into third
In reaction solution.Reaction solution can be made to be constantly in optimal equilibrium state using such injection system, advantageously form grain
The uniform quantum dot of diameter.
Further, wiring solution-forming is distinguished into the second sulphur source and the second zinc source, it can be using the 7th non-complexing solvent by the
The dissolution of two sulphur sources and wiring solution-forming, and the second zinc source is dissolved by simultaneously wiring solution-forming using the 8th non-complexing solvent.When the second sulphur source
With the second zinc source be solution when, the 7th non-complexing solvent or the 8th non-complexing solvent can be omitted.
Further, the second sulphur source and the molar ratio in the second zinc source can be (0.1~1): 1.
Step S170: the 4th reaction solution is purified, quantum dot is obtained.
Further, step S170 includes: the 4th reaction solution to be down to room temperature, and use the volume ratio of methanol and n-butanol
For 1:(1~5) mixed solvent the 4th reaction solution is precipitated, obtain sediment.Sediment is dissolved in toluene again, is obtained
To quantum dot.
The first used indium source, the first phosphorus source, the second indium source, the second phosphorus source, selenium in the preparation step of above-mentioned quantum dot
Source, the first sulphur source, the first zinc source, the second sulphur source and the second zinc source can be the conventional kind of this field.
Specifically, the first indium source and the second indium source used in the preparation step of above-mentioned quantum dot are separately selected from
Oleic acid indium, carbonic acid indium, indium nitrate, indium acetate, stearic acid indium, indium iodide, indium bromide, trimethyl indium, inidum chloride and tetradecylic acid indium
At least one.
Specifically, above-mentioned first phosphorus source and the second phosphorus source are separately selected from three (dimethylamino) phosphines, three (diethylamine
At least one of base) phosphine, three (trimethylsilyl) phosphines, tri octyl phosphine and tributylphosphine.
Specifically, above-mentioned first zinc source and the second zinc source are separately selected from zinc laurate, Zinc tetradecanoate, two thio
Carbaminate, diethyl zinc, zinc methide, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, carbon
Sour zinc, zinc cyanide, zinc nitrate, zinc oleate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, caproic acid zinc, zinc octoate, palm
At least one in sour zinc, ten sour zinc, zinc undecylenate, diethyldithio-carbamate zinc, Zinc diacetate dihydrate and zinc stearate
Kind.
Specifically, above-mentioned first sulphur source and the second sulphur source are separately selected from sulphur simple substance, alkyl hydrosulfide, six ammonia of hydrogen sulfide
At least one of base thioether and bis- (trimethyl silicon substrate) thioethers.
Specifically, above-mentioned selenium source is selected from trioctylphosphine selenizing phosphine, three (normal-butyl) selenizing phosphines, three (sec-butyl) selenizing phosphines, three
(tert-butyl) selenizing phosphine, trimethyl selenizing phosphine, triphenyl selenizing phosphine, diphenyl selenizing phosphine, phenylselenenylation phosphine, thricyclohexyl selenizing
Phosphine, cyclohexyl selenizing phosphine, the pungent selenol of 1-, 1- dodecane selenol, selenium phenol, selenium simple substance, hydrogen selenide, bis- (trimethyl silyl) selenium
At least one of compound and selenourea.
The first used non-complexing solvent, the second non-complexing solvent, the non-network of third in the preparation step of above-mentioned quantum dot
Bonding solvent, the 4th non-complexing solvent, the 5th non-complexing solvent, the 6th non-complexing solvent, the 7th non-complexing solvent and the 8th non-network
Bonding solvent is separately selected from least one of alkene, alkane, ether and aromatic compound.Further, the first non-network
Bonding solvent, the second non-complexing solvent, third non-complexing solvent, the 4th non-complexing solvent, the 5th non-complexing solvent, the 6th non-complexing
Solvent, the 7th non-complexing solvent and the 8th non-complexing solvent be each independently selected from phenylbenzene, octadecylene, 19 alkene, icosa alkene,
At least one of lignocerane, docosane, eicosane, octadecane, atoleine and isotriacontane.
The first used ligand and Ligands can be separately acidity in the preparation step of above-mentioned quantum dot
Ligand.Further, the first ligand and Ligands are separately selected from ten acid, undecenoic acid, lauric acid/dodecanoic acid, tridecanoic acid, ten
At least one of tetracid, hexadecylic acid, stearic acid, octadecyl phosphoric acid and oleic acid.
By the preparation method of above-mentioned cadmium-free quantum dots, crystalline substance is formed under certain reaction condition first with indium source and phosphorus source
Kind, then so that crystal seed is grown into nucleus under certain reaction condition, the quantum dot core that component is P elements and phosphide element is obtained,
Again by epitaxial growth method, ZnSeS hypostracum and ZnS outer shell are coated on the quantum dot core, obtains InP/ZnSeS/ZnS amount
Son point product.There is core-shell structure by the cadmium-free quantum dots that above-mentioned preparation method obtains.Wherein, the composition member of the material of stratum nucleare
Element includes P elements and phosphide element, and shell includes the hypostracum being coated on stratum nucleare and the outer shell that is coated on hypostracum, interior
The material of shell is ZnSeS, and the material of outer shell is ZnS.The particle size of prepared cadmium-free quantum dots be 6nm~
The radius of 12nm, the stratum nucleare are 1.2nm~4.5nm, and in 510nm~650nm, half-peak breadth is the wave-length coverage of fluorescence emission peak
35nm~40nm, luminous efficiency are 70%~85%.
The preparation method of above-mentioned cadmium-free quantum dots has at least the following advantages:
(1) preparation method of above-mentioned cadmium-free quantum dots has the advantages that easy to operate, result is stable, favorable repeatability.
(2) the half-peak width for the cadmium-free quantum dots that the preparation method of above-mentioned cadmium-free quantum dots enables to, luminous efficiency
Height, and using the preparation method of above-mentioned cadmium-free quantum dots, it still can achieve same result when expanding volume production.
(3) by change molar ratio, injection rate, reaction temperature etc., the wavelength and band structure of quantum dot can be adjusted,
Be conducive to further increase luminous efficiency.
Present invention will be further explained by specific examples below, but is not used in the limitation present invention.
In following embodiment and comparative example, the particle size of quantum dot and the radius of stratum nucleare use model JEM-
2100TEM transmissioning electric mirror test, test condition are as follows: at 25 DEG C, 1 μ L quantum dot solution is taken to be dispersed in the glass for filling 25ml toluene
In glass bottle, closeing the lid, oscillation shakes up, and the quantum dot solution after dispersion is drawn with syringe, is dripped on the copper mesh of 3mm, to
After drying, drop is repeated twice, be put into sample injector, tested after dry.
The fluorescence emission peak of quantum dot, half-peak breadth are tested using model Cary Eclipse sepectrophotofluorometer, are surveyed
Strip part are as follows: under the conditions of 25 DEG C, take 3 μ L quantum dot solutions to be distributed in the vial for filling the toluene of 2.5mL, close the lid
It shakes up, is then transferred in 3mL quartz colorimetric utensil, is closed the lid with dropper, open the toluene baseline tested, tested.
The ultraviolet and visible absorption peak of quantum dot is tested using 4000 ultraviolet-uisible spectrophotometer of model Cary, test
Condition are as follows: under the conditions of 25 DEG C, take 3 μ L quantum dot solutions to be distributed in the vial for filling the toluene of 2.5mL, close the lid and shake
It is even, it is then transferred in 3mL quartz colorimetric utensil, is closed the lid with dropper, opened the toluene baseline tested, tested.
The luminous efficiency of quantum dot is using model Labsphere QEMS-2000-PL integrating sphere fluorescent quantum test system
Unified test examination, test condition are as follows: under the conditions of 25 DEG C, take 1mL quantum dot solution to be added in glue, stirred under the rate of 300rpm
5min vacuumizes 10min, and quantum dot is then mixed glue coated on film, solidifies 30s, quantum dot diaphragm is made, is put into instrument
In sample cell, tested.
Embodiment 1
The preparation process of the quantum dot of the present embodiment is as follows:
(1) by 13mmol oleic acid, 5mmol octadecyl phosphoric acid and 255mmol octadecylene Hybrid Heating to 80 DEG C, is obtained
One mixed liquor.And degasification 30min is carried out, reaction later carries out under protection of argon gas.It simultaneously will with the rate of 15mL/min
5.2mmol trimethyl indium solution (being dissolved in 52mmol octadecylene) and 13mmol tri- (trimethylsilyl) phosphine solution (are dissolved in
In 20mmol octadecylene) it is injected into the first mixed liquor simultaneously, and temperature is raised to 100 DEG C and carries out the first reaction 10min, it obtains
First reaction solution.
(2) temperature is risen to 250 DEG C, by 8.67mmol trimethyl indium solution (being dissolved in 100mmol octadecylene) and
(trimethylsilyl) phosphine of 8.67mmol tri- solution (being dissolved in 100mmol octadecylene) is with V1=0.2mL/min (injection
10min), V2=0.4mL/min (injection 10min), V3It is anti-that the rate of=0.6mL/min (injection 10min) is injected into first simultaneously
It answers in liquid, carries out the second reaction 30min, be down to room temperature, obtain containing the InP quantum dot core (molar ratio of P elements and phosphide element
For the second reaction solution of 1:1).
(3) by 17mmol zinc stearate, 15mmol oleic acid and 55mmol isotriacontane Hybrid Heating to 130 DEG C, the is formed
Two mixed liquors, and degasification 60min, reaction later carry out under protection of argon gas.270 DEG C are warming up to, first with the speed of 15mL/min
The second reaction solution of 30mL is injected into the second mixed liquor by rate, then with the rate of 0.1mL/min by 33mmol selenizing diisobutyl
The mixed solution of phosphine and bis- (trimethyl silicon substrate) thioethers of 33mmol is injected into the second mixed liquor, and it is anti-that third is carried out at 330 DEG C
30min is answered, to form the ZnSeS shell being coated on InP core, obtains third reaction solution.
(4) again simultaneously with V1'=0.5mL/min (injection 15min), V2'=1.0mL/min (injection 15min), V3'=
Bis- (trimethyl silicon substrate) the thioether solution of 57mmol zinc oleate and 12mmol (are dissolved in by the rate of 1.5mL/min (injection 15min)
In 120mmol octadecylene) it is injected into third reaction solution, the 4th reaction 45min is carried out at 330 DEG C, is coated on being formed
ZnS shell on ZnSeS shell, obtains the 4th reaction solution.
(5) the 4th reaction solution is down to room temperature, is then added with the mixed solvent that the volume ratio of methanol and n-butanol is 1:3
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
InP/ZnSeS/ZnS quantum dot.Wherein, InP is the stratum nucleare of quantum dot, and ZnSeS is the hypostracum of quantum dot, and ZnS is quantum
The outer shell of point, "/" expression layer.Test particle size, the stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth of the quantum dot
And luminous efficiency, test result are listed in table 1, fluorescence spectra is as shown in Figure 2.
Embodiment 2 expands volume production experiment
The preparation process of the quantum dot of the present embodiment is as follows:
(1) 78mmol oleic acid, 30mmol octadecyl phosphoric acid and 1350mmol octadecylene Hybrid Heating are obtained to 80 DEG C
First mixed liquor.And degasification 30min is carried out, reaction later carries out under protection of argon gas.Simultaneously with the rate of 90mL/min
31.2mmol trimethyl indium solution (being dissolved in 312mmol octadecylene) and 78mmol tri- (trimethylsilyl) phosphine solution is (molten
Solution is in 120mmol octadecylene) it is injected into the first mixed liquor simultaneously, and temperature is raised to 100 DEG C and carries out the first reaction
10min obtains the first reaction solution.
(2) temperature is risen to 250 DEG C, by 52.02mmol trimethyl indium solution (being dissolved in 600mmol octadecylene) and
(trimethylsilyl) phosphine of 52.02mmol tri- solution (being dissolved in 600mmol octadecylene) is with V1=1.2mL/min (injection
10min), V2=2.4mL/min (injection 10min), V3It is anti-that the rate of=3.6mL/min (injection 10min) is injected into first simultaneously
It answers in liquid, carries out the second reaction 30min, be down to room temperature, obtain containing the InP quantum dot core (molar ratio of P elements and phosphide element
For the second reaction solution of 1:1).
(3) it by 510mmol zinc stearate, 450mmol oleic acid and 1650mL isotriacontane Hybrid Heating to 130 DEG C, is formed
Second mixed liquor, and degasification 60min, reaction later carry out under protection of argon gas.270 DEG C are warming up to, first with 200mL/min's
The second reaction solution of 120mL is injected into the second mixed liquor by rate, then with the rate of 3mL/min by two isobutyl of 990mmol selenizing
The mixed solution of base phosphine and bis- (trimethyl silicon substrate) thioethers of 990mmol is injected into the second mixed liquor, and third is carried out at 330 DEG C
30min is reacted, to form the ZnSeS shell being coated on InP core, obtains third reaction solution.
(4) again simultaneously with V1'=15mL/min (injection 15min), V2'=30mL/min (injection 15min), V3'=
The rate of 45mL/min (injection 15min) (dissolves bis- (trimethyl silicon substrate) the thioether solution of 1710mmol zinc oleate and 36mmol
In 3600mmol octadecylene) it is injected into third reaction solution, the 4th reaction 45min is carried out at 330 DEG C, is coated on being formed
ZnS shell on ZnSeS shell, obtains the 4th reaction solution.
(5) the 4th reaction solution is down to room temperature, is then added with the mixed solvent that the volume ratio of methanol and n-butanol is 1:3
Into the 4th reaction solution, quantum dot is precipitated, and be centrifuged, obtains sediment.Sediment is dissolved in toluene, is obtained after purification
InP/ZnSeS/ZnS quantum dot.Test particle size, the stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth of the quantum dot
And luminous efficiency, test result are listed in table 1.
Embodiment 3
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, under conditions of injecting same volume, area
It is not, in step (1), the injection speed of trimethyl indium solution and three (trimethylsilyl) phosphine solution is 8mL/min.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Embodiment 4
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, under conditions of injecting same volume, area
It is not, in step (2), the injection speed of trimethyl indium solution and three (trimethylsilyl) phosphine solution is always 0.2mL/min.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Embodiment 5
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, under conditions of injecting same volume, area
It is not, in step (3), the injection speed of the second reaction solution is 8mL/min, selenizing diisobutyl phosphine and bis- (trimethyl silicon substrates)
The injection speed of the mixed solution of thioether is 0.3mL/min.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Embodiment 6
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, under conditions of injecting same volume, area
It is not, in step (4), the injection speed of zinc oleate and bis- (trimethyl silicon substrate) thioether solution is always 1mL/min.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Embodiment 7
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, and difference is, in step (1), first is anti-
The condition answered are as follows: temperature is 70 DEG C, time 10min；In step (2), the condition of the second reaction are as follows: temperature is 240 DEG C, the time
For 30min；In step (3), the condition of third reaction are as follows: temperature is 250 DEG C, time 30min；In step (4), the 4th reaction
Condition are as follows: temperature be 250 DEG C, time 45min.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Embodiment 8
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, and difference is, in step (1), first is anti-
The condition answered are as follows: temperature is 130 DEG C, time 10min；In step (2), the condition of the second reaction are as follows: temperature is 300 DEG C, when
Between be 30min；In step (3), the condition of third reaction are as follows: temperature is 350 DEG C, time 30min；In step (4), the 4th is anti-
The condition answered are as follows: temperature is 350 DEG C, time 45min.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Embodiment 9
The preparation process of the quantum dot of the present embodiment is roughly the same with embodiment 1, and difference is, in step (1), first is mixed
It closes and is free of octadecyl phosphoric acid in liquid, specifically: by 13mmol oleic acid and 255mmol octadecylene Hybrid Heating to 80 DEG C, obtain
First mixed liquor.
Particle size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and the luminous efficiency of the quantum dot are tested, is surveyed
Test result is listed in table 1.
Comparative example 1
(1) synthesis of InP nanocluster: 0.13mmol tetradecylic acid indium, 0.1mmol lauric acid/dodecanoic acid and 2g isotriacontane are mixed
140 DEG C are heated to, after stablizing 10min, 90 DEG C is cooled to, (trimethyl silicane) phosphine of 0.045mmol tri- and tri- fourth of 0.045mmol is added
Base phosphine keeps the temperature 5min at 90 DEG C, obtains the first mixed liquor of the nanocluster containing InP.
The synthesis of (2) the 2nd InP cores: 0.27mmol indium acetate, 0.8mmol tetradecylic acid and 6g octadecylene are mixed and heated to
230 DEG C of heat preservations, are added (trimethyl silicane) phosphine of 0.09mmol tri- and 0.09mmol octylame, keep the temperature 8min at 230 DEG C, obtain containing the
Second mixed liquor of one InP core.At 230 DEG C, the first mixed liquor of abovementioned steps synthesis is added in the second mixed liquor, the used time
The third mixed liquor containing the 2nd InP core after growth is made in 10min.
(3) the cladding synthesis of InP/ZnSe/ZnS: the temperature of the third mixed liquor containing the 2nd InP core is stablized to 250
DEG C, and add again after 0.3mmol zinc stearate, 0.6mmol oleic acid, 0.09mmol selenium-tri octyl phosphine reaction 10min are added thereto
Enter 0.21mmol sulphur-tri octyl phosphine, after keeping the temperature 30min at 250 DEG C, is down to room temperature and obtains the product containing InP/ZnSe/ZnS
System extracts the product system three times with methanol, obtains extract；With the acetone precipitation extract, and sediment is centrifuged, so
The precipitating obtained after centrifugation is dissolved in toluene afterwards, obtains InP/ZnSe/ZnS quantum dot solution.Test the grain of the quantum dot
Diameter size, stratum nucleare radius, the wavelength of fluorescence emission peak, half-peak breadth and luminous efficiency, test result are listed in table 1.
Table 1
| Partial size/nm | Stratum nucleare radius/nm | Emission peak wavelength/nm | Half-peak breadth/nm | Luminous efficiency/% | |
| Embodiment 1 | 11.2 | 3.3 | 632 | 35 | 85 |
| Embodiment 2 | 11.5 | 3.6 | 632 | 35 | 85 |
| Embodiment 3 | 8.6 | 2.8 | 608 | 37 | 82 |
| Embodiment 4 | 9.4 | 3.2 | 616 | 38 | 80 |
| Embodiment 5 | 10.3 | 4.1 | 622 | 39 | 78 |
| Embodiment 6 | 7.8 | 1.5 | 573 | 38 | 79 |
| Embodiment 7 | 8.1 | 2.7 | 595 | 36 | 77 |
| Embodiment 8 | 6.6 | 1.8 | 562 | 39 | 75 |
| Embodiment 9 | 8.8 | 3.5 | 538 | 40 | 74 |
| Comparative example 1 | 3.5 | 1.5 | 605 | 47 | 64 |
Seen from table 1, the half-peak breadth of quantum dot of the invention is relatively narrow and luminous efficiency is higher, and compared to comparative example 1
Method, the preparation method of quantum dot of the invention is easy to operate without preparing InP nanocluster, and stability is high.By embodiment 1
It is also found that method of the invention still can achieve same result when expanding volume production with the result of embodiment 2.
Each technical characteristic of embodiment described above can be combined arbitrarily, for simplicity of description, not to above-mentioned reality
It applies all possible combination of each technical characteristic in example to be all described, as long as however, the combination of these technical characteristics is not deposited
In contradiction, all should be considered as described in this specification.
The embodiments described above only express several embodiments of the present invention, and the description thereof is more specific and detailed, but simultaneously
It cannot therefore be construed as limiting the scope of the patent.It should be pointed out that coming for those of ordinary skill in the art
It says, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to protection of the invention
Range.Therefore, the scope of protection of the patent of the invention shall be subject to the appended claims.
Claims (10)
1. a kind of cadmium-free quantum dots, which is characterized in that including stratum nucleare and shell, the component of the material of the stratum nucleare includes phosphorus
Element and phosphide element, the shell include the hypostracum being coated on the stratum nucleare and the shell that is coated on the hypostracum
Layer, the material of the hypostracum are ZnSeS, and the material of the outer shell is ZnS；The particle size of the cadmium-free quantum dots is
The radius of 6nm~12nm, the stratum nucleare are 1.2nm~4.5nm, and the wave-length coverage of the fluorescence emission peak of the cadmium-free quantum dots exists
510nm~650nm, half-peak breadth are 35nm~40nm, and luminous efficiency is 70%~85%.
2. cadmium-free quantum dots according to claim 1, which is characterized in that the radius of the stratum nucleare accounts for the cadmium-free quantum dots
Radius ratio be 40%~75%.
3. cadmium-free quantum dots according to claim 1, which is characterized in that in the stratum nucleare, the P elements and the indium
The molar ratio of element is (0.1~3): 1.
4. a kind of preparation method of cadmium-free quantum dots, which comprises the steps of:
First indium source, the first phosphorus source are mixed with the first mixed liquor, and reacted at 70 DEG C~150 DEG C, the first reaction solution is obtained,
Contain the first ligand, the first non-complexing solvent and optional crystal seed stabilizer in first mixed liquor；
Second indium source, the second phosphorus source are mixed with first reaction solution, and reacted at 200 DEG C~300 DEG C, it is anti-to obtain second
Answer liquid；
Selenium source, the first sulphur source, second reaction solution and the second mixed liquor are mixed, and carried out instead at 200 DEG C~350 DEG C
It answers, obtains third reaction solution, contain the first zinc source, Ligands and the 6th non-Lip river bonding solvent in second mixed liquor；And
Second sulphur source, the second zinc source are mixed with the third reaction solution, and reacted at 200 DEG C~350 DEG C, the amount of obtaining
Sub- point.
5. according to the method described in claim 4, it is characterized in that, described by the first indium source, the first phosphorus source and the first mixed liquor
The step of mixing includes: that first indium source and the first phosphorus source are distinguished wiring solution-forming, then with 10mL/min~200mL/min's
Rate is injected into simultaneously in first mixed liquor.
6. according to the method described in claim 4, it is characterized in that, described that second indium source, the second phosphorus source and described first is anti-
The step of answering liquid to mix includes: that second indium source and the second phosphorus source are distinguished wiring solution-forming, then successively with V1、V2To VxSpeed
Rate divides x stage injection into first reaction solution, wherein V1=0.1mL/min~1.5mL/min, the Speedometer Drive of m-stage
It is shown as Vm, Vm/V1=1+mp-p, p=0.8~1.2.
7. the preparation method of quantum dot according to claim 4, which is characterized in that it is described by selenium source, it is the first sulphur source, described
The step of second reaction solution and the second mixed liquor mix includes: first with the rate of 10mL/min~400mL/min by described second
Reaction solution is injected into second mixed liquor, then with the rate of 0.01mL/min~5mL/min by the selenium source and the first sulphur
Source is injected into second mixed liquor.
8. according to the method described in claim 4, it is characterized in that, described that second sulphur source, the second zinc source and the third is anti-
The step of answering liquid to mix includes: that wiring solution-forming is distinguished in second sulphur source and the second zinc source, then successively with V1’、V2' to Vy'
Rate divides y stage injection into the third reaction solution, wherein V1'=0.1mL/min~20mL/min, the rate of n-th order section
It is expressed as Vn', Vn’/V1'=1+np '-p ', p '=0.8~1.2.
9. according to the method described in claim 4, it is characterized in that, first indium source and the second indium source are separately selected from
Oleic acid indium, carbonic acid indium, indium nitrate, indium acetate, stearic acid indium, indium iodide, indium bromide, trimethyl indium, inidum chloride and tetradecylic acid indium
At least one；And/or
First phosphorus source and the second phosphorus source are separately selected from three (dimethylamino) phosphines, three (diethylin) phosphines, three (front threes
At least one of silylation) phosphine, tri octyl phosphine and tributylphosphine；And/or
First zinc source and the second zinc source be separately selected from zinc laurate, Zinc tetradecanoate, zinc dithiocarbamate,
Diethyl zinc, zinc methide, zinc acetate, zinc acetylacetonate, zinc iodide, zinc bromide, zinc chloride, zinc fluoride, zinc carbonate, cyaniding
Zinc, zinc nitrate, zinc oleate, zinc oxide, zinc peroxide, zinc perchlorate, zinc sulfate, caproic acid zinc, zinc octoate, zinc palmitate, ten acid
At least one of zinc, zinc undecylenate, diethyldithio-carbamate zinc, Zinc diacetate dihydrate and zinc stearate；And/or
First sulphur source and the second sulphur source are separately selected from sulphur simple substance, alkyl hydrosulfide, six amino thioether of hydrogen sulfide and double
At least one of (trimethyl silicon substrate) thioether；And/or
The selenium source is selected from trioctylphosphine selenizing phosphine, three (normal-butyl) selenizing phosphines, three (sec-butyl) selenizing phosphines, three (tert-butyl) selenizings
Phosphine, trimethyl selenizing phosphine, triphenyl selenizing phosphine, diphenyl selenizing phosphine, phenylselenenylation phosphine, thricyclohexyl selenizing phosphine, cyclohexyl selenium
Change phosphine, the pungent selenol of 1-, 1- dodecane selenol, selenium phenol, selenium simple substance, hydrogen selenide, bis- (trimethyl silyl) selenides and selenourea
At least one of；And/or
The first non-complexing solvent is selected from phenylbenzene, octadecylene, 19 alkene, icosa alkene, lignocerane, docosane, 20
At least one of alkane, octadecane, atoleine and isotriacontane；And/or
First ligand is selected from ten acid, undecenoic acid, lauric acid/dodecanoic acid, tridecanoic acid, tetradecylic acid, hexadecylic acid, stearic acid, octadecyl
At least one of phosphoric acid and oleic acid；And/or
The crystal seed stabilizer is selected from least one of octadecyl phosphoric acid and trioctylphosphine.
10. according to the method described in claim 4, it is characterized in that, first ligand, the first non-complexing solvent and institute
The molar ratio for stating crystal seed stabilizer is 1:(2~20): (0~3)；And/or
The molar ratio in first indium source, first phosphorus source and first ligand is 1:(0.1~3): (1~5)；And/or
The molar ratio of second indium source and second phosphorus source is 1:(0.5~2)；And/or
The selenium source, first sulphur source and the molar ratio in first zinc source are (1~3): (1~3): 1；And/or
The molar ratio in first zinc source, the Ligands and the 6th non-complexing solvent is 1:(0.5~2): (1~5)；With/
Or,
Second sulphur source and the molar ratio in second zinc source are (0.1~1): 1.
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